Chlorophenoxyethyl esters of diallylthionocarbamic acid



United States Patent 2 Claims. (Cl. 260-455) This is a division ofapplication Serial No. 844,872,

filed October 7, 1959, now U.S. Patent No. 3,142,693.

The present invention relates to new compounds and more particularly toaryloxyethyl esters of diallylthiocarbamic acids.

The compounds of the present invention may be represented by the generalformula where R represents phenyl or halogen substituted pbenyl, Yrepresents oxygen or sulfur, X and X represent oxygen or sulfur at leastone of which is sulfur and R and R" represent allyl or chloroallyl.Typical examples of the preferred compounds comprise2-(phenylthio)ethyl, 2- (phenoxy)ethyl, 2-(p-chlorophenylthio)ethyl, 2-(p-chlorophenoxy)ethyl, 2-(p-br0m0pl1enylthio)ethyl,Z-(p-bromophenoxy)ethyl, 2-(2,4-dichlorophenylthio)ethyl, 2 (2,4-dibromophenylthio)ethyl, 2'-(2,4 dichlorophenoxy)ethyl,2-(2,4-dibromophenoxy)ethyl, 2-(2,4,5 trichlorophenylthio)ethy1 and2-(2,4,5-trichlorophenoxy)ethyl esters of diallyldithiocarbamic acid,diallylthiolcarbamic acid and diallylthionocarbamic acid.

Although other methods of preparation are suitable, such thiocarbamatesmay be conveniently obtained by converting diallylamine to athiocarbamic acid and condensing the diallylthiocarbamic acid with thehalide containing the desired ether substituent. As an illustration of asatisfactory procedure, 23 grams (0.3 mole) of carbon bisulfide wasadded dropwise with stirring to 68 grams (0.7 mole) of diallylaminedissolved in 150 ml. of dimethyl formarnide, the mixture being kept at-25 C. during the addition. Then 56 grams (0.3 mole) ofp-chlorophenoxyethyl chloride was added in one portion and the mixturestirred for 5 hours at 6070 C. After cooling to room temperature, 250ml. ofwater were added to the product and the water solution extractedwith 250 ml. of ether. The organic layer which separated was washed with300 ml. of water and dried over sodium sulfate. The solvent was removedby stripping at 90-100 C. (14 mm. pressure). The2-(p-chlorophenoxy)ethyl diallyldithiocarbamate, obtained in theoryyield, was an amber oil analyzing 4.6% nitrogen, 10.9% chlorine and19.8% sulfor as compared to 4.3% nitrogen, 10.8% chlorine and 19.6%sulfur calculated for C I-I ClNOS A solution of 14.7 grams (0.15 mole)of monochloroacetic acid in 50 ml. of water Was carefully neutralizedwith 10.4 grams of potassium carbonate. The solution was cooled to 5 C.and added in one portion to 0.15 mole of a potassium xanthate from analcohol containing the desired phenoxy ethyl group. The reaction mixturewas stirred for one hour at room temperature and to it was then added19.5 grams of diallylamine. Stirring was continued for 4 hours afterwhich the reaction mixture was extracted with ether, the ether extractsdried over sodium sulfate and the ether removed in vacuo. Productsobtained by this procedure after removing volatile constituents byheating to 90-100" C. under 12 mm. Hg pressure are summarized below:

Product Yield, Xanthate Reaetant percent i 2-(Phenylthio)ethyl diallyl-87. 6 @SC2H4O C-SK thionocarbamate.

I [l 2-(2,4,S-Trichlorophenoxy)- 74. 6 Cl 0 CzHaO C-SK ethyldiallylthionocarbamate. C1

C1 i 2-(2,4-Dichlor0phenoxy)- 71. 7 o10 CzHiCSK ethyldiallylthionocarbarnate.

The new compounds exert significant biological activity. In general theyare efiicient herbicides which combine grass and broadleaf activity.They are particularly efiective in preemergent application. Amountswithin the range of 1 to pounds per acre are adequate for most purposes.The toxicants may be applied in the form of a spray containing theactive ingredient in a concentration within the range of ODS-5.0%. Whilethe active components are insoiuble in water they are soluble in commonorganic solvents. They may be dispersed directly in water or dissolvedfirst in an organic solvent and then dispersed. As dispersing andwetting agents there may be employed soft or hard sodium or potassiumsoaps, alkylated aromatic sodium sulfonates such as sodiumdodecylbenzenesulfonate, or an amine salt thereof, alkali metal salts ofsulfated fatty alcohols, ethylene oxide condensation products of alkylphenols, tall oil, higher alcohols or higher mercaptans. The solidformulations or dust may contain in addition to the active ingredient,diluents or extenders, preferably those which render the formulationspermanently dry and free flowing. Effective solid diluents are clay,talc, pyrophyllite, silica and fullers earth.

As illustrative of the herbicidal activity the ester was emulsified inwater and the emulsion applied as a spray. In this manner the activeingredient was applied to the soil of seeded plots before any plantsemerged. About fourteen days after application of the toxicants resultswere observed and recorded. The number of seeds emerging was convertedto weighted herbicidal ratings based on average percent germination ofany particular seed lot times an injury factor. This evensirregularities of ratings on seeds which may vary in percentgermination. The injury factor takes into consideration any plants notexpected to survive. Thus, phytotoxicity ratings are based on the numberof plants which emerge and will survive as 9 observed two Weeks afterplanting. Herbicidal ratings were assigned by means of the followingconversion scale:

Percent emergence: Phytotoxicity rating -25 3 or severe.

26-50 2 or moderate. 51-75 1 or slight. 76-100 0 or none.

Table I illustrates per-emergent herbicidal activity of typicalcompounds at 5 pounds per acre:

Table I Active Ingredient Results Observed2-(2,4,5-Triehlorophenoxy)-ethyl ,Severe phytotoxieity to morningdiallylthionocarbamate.

2-(2,4-Dichlorophenoxy) ethyl diallylthionoearbamate.

2- (2 ,-Diehlorophenoxg') ethyl btibs (2-ehloroal1yl) dithiocarbama e.

It is intended to cover all changes and modifications of the examples ofthe invention herein chosen for purposes of disclosure which do notconstitute departures from the spirit and scope of the invention.

What is claimed is:

1. 2 (2,4 dichlorophenoxy)ethyl diallylthionocarbamate.

2. 2-( 3,4,5 trichlorophenoxy)ethyl diallylthionocarbamate.

References Cited by the Examiner UNITED STATES PATENTS 2,941,879 6/60Goodhue 712.7 2,992,091 7/61 Harman et a1. 712.6 3,055,751 9/62 Tilleset a1. 712.3 X

FOREIGN PATENTS 219,675 2/58 Australia.

OTHER REFERENCES Nature, vol. 176, pages 308 to 310, Aug. 13, 1955.

CHARLES B. PARKER, Primary Examiner.

JULIAN S. LEVITT, Examiner.

1. 2 - (I,4 - DICHLOROPHENOXY)ETHYL DIALLYTHIONCARBAMATE.
 2. 2-(3,4,5 -TRICHLOROPHENOXY)ETHYL DIALLYLTHIONCARBAMATE.